Field ion microscopy uses a high electric field to ionize gas atoms on the tip of a sample, which are then detected to create an atomic-scale image of the sample surface. Infrared spectroscopy analyzes the absorption of infrared light by molecules to determine their structure. Raman spectroscopy analyzes the inelastic scattering of monochromatic light when it interacts with molecular vibrations, rotations, and other low frequency modes to provide molecular fingerprint information. Both techniques produce spectra that can be used to identify chemicals based on the frequencies of molecular vibrations they produce.

1. FIELD –ION MICROSCOPY
INFRARED AND RAMAN SPECTROSCOPY
PRESENTED BY:
SAMEER VISHWAKARMA
M.Tech.( Production )
IV Semester
SUBMITTED TO-
DR. PRADEEP KUMAR SINGH
DEPTT. OF MECH. ENGG.

2. OUTLINES-
 Introduction
 Working Principle
 Instrument Description
 Working

3. Field Ion Microscopy

4. Introduction to FIM
 The Field ion microscope (FIM) was invented by Muller in
1951.
 It is a type of microscope that can be used to image the
arrangement of atoms at the surface of a sharp metal tip.

5. Working Principle of FIM
 The basic principle of FIM is on ionization of the
gases and tracking ions with a tracking device.
 In FIM, the needle tip like sample is prepared,
put in a high vacuum chamber backfilled with
imaging gas(helium or neon) and when a high
voltage of range 5-10KV is applied the gases
adsorbed on the tip of sample get ionized and
repelled in direction perpendicular to the tip
surface. These ions are tracked by a probe or
projected on a screen to get final image.
 The curvature of the surface near the tip causes
a natural magnification by point projection
effect.
TIP: Have you even seen your
face in concave/convex mirror?

6. Instrument and Working of FIM
 Image is produced by applying high
voltage to specimen with respect to
channel plate screen in presence of
imaging gas .
 The field strength required at the
sample surface reaches approximately
50v/nm.
 In order to achieve this order of
magnitude needle shaped specimens are
prepared with average radius of
curvature R=10-100nm.

7.  The whole setup is kept in ultra high
vacuum at a pressure of 10ˆ-7 pa.
 During the operation tip is kept at
temperature of 10- 150k
 Imaging system comprises of micro channel
plate and phosphor screen.
 The applied field at which field image results is called Best Image Field
(BIF) and the corresponding voltage is called Best Image Voltage(BIV).
 Advantages of field evaporation > Removal of oxides and impurities on the
surface of sample. > smoothens the irregular surface of the sample until the
hemispherical surface is obtained.

8. Infra-Red Spectroscopy

9. Introduction to IR Spectroscopy
 Infrared spectroscopy (IR spectroscopy) is the spectroscopy that
deals with the infrared region of the electromagnetic spectrum,
that is light with a longer wavelength and lower frequency than
visible light. It covers a range of techniques, mostly based on
absorption spectroscopy.
 Infrared spectroscopy (IR spectroscopy or vibration spectroscopy)
involves the interaction of infrared radiation with matter.
 It covers a range of techniques, mostly based on absorption
spectroscopy.
 It can be used to identify and study chemicals. Samples may be
solid, liquid, or gas

10. Working Principle of IR Spectroscopy
 The IR spectroscopy theory exploits that
the fact that molecules absorb specific
frequencies that are characteristic of
their structure. The energies are
determined by the shape of the molecular
potential energy surfaces, the masses of
the atoms and the associated vibronic
coupling.
 For instance, the molecule can absorb the
energy contained in the incident light and
the result is a faster rotation or a more
pronounced vibration.
DIRECTION SYMMETRIC ASYMMETRIC
RADIAL
Symmetric
stretching
Antisymmetric
stretching
LATITUDINAL
Scissoring Rocking
LONGOTUDIANAL
Wagging Twisting
Molecular Vibrations

11. Instruments and Working of IR Spectroscopy
 The main parts of IR spectrometer are as
follows:
 Radiation source
 Sample cells and sampling of substances
 Monochromators
 Detectors
 Recorder

12. Radiation Sources
 IR instruments require a source of radiant energy which emit IR
radiation which must be sufficient intensity, continuous and stable.
 Sources of IR radiations are as follows:
 GLOBAR
 NERNST GLOBAR

13. Sample Cell
 For gas samples: The spectrum of a gas can be
obtained by permitting the sample to expand into
an evacuated cell, also called a cuvette.
 For solution sample: Infrared solution cells consists
of two windows of pressed salt sealed. Samples that
are liquid at room temperature are usually analyzed
in pure form or in solution. The most common
solvents are Carbon Tetrachloride (CCl4) and Carbon
Disulfide (CS2).
 For solid sample: Solids reduced to small particles
(less than 2 micron) can be examined as a thin paste
or mull. The mull is formed by grinding a 2-5
milligrams of the sample in the presence of one or
two drops of a hydrocarbon oil (nujol oil). The
resulting mull is then examined as a film between
flat salt plates
CUVETTE
CELL FOR SOLUTION
CELL FOR SOLID

14. Monochromators
Thermal and Non thermal detectors and recorders are used
for imaging.

15. Working
An infrared spectrophotometer is an instrument that passes
infrared light through an organic molecule and produces a
spectrum that contains a plot of the amount of light transmitted
on the vertical axis against the wavelength of infrared radiation
on the horizontal axis. In infrared spectra the absorption peaks
point downward because the vertical axis is the percentage
transmittance of the radiation through the sample.
Absorption of radiation lowers the percentage transmittance
value. Since all bonds in an organic molecule interact with
infrared radiation, IR spectra provide a considerable amount of
structural data.

16. RAMAN SPECTROSCOPY

17. Introduction to Raman Spectroscopy
 When radiation passes through a transparent medium, the
species present scatter a fraction of the beam in all
directions.
 In 1928, the Indian physicist C. V. Raman discovered that the
visible wavelength of a small fraction of the radiation
scattered by certain molecules differs from that of the
incident beam and furthermore that the shifts in wavelength
depend upon the chemical structure of the molecules
responsible for the scattering.
 The theory of Raman scattering shows that the phenomenon
results from the same type of quantized vibrational changes
that are associated with infrared absorption. Thus, the
difference in wavelength between the incident and
scattered visible radiation corresponds to wavelengths in the
mid-infrared region.
 The Raman scattering spectrum and infrared absorption
spectrum for a given species often resemble one another
quite closely.

18. Working Principle of Raman Spectroscopy
 Raman spectra are acquired by irradiating a sample with a powerful laser source of
visible or near-infrared monochromatic radiation. During irradiation, the spectrum
of the scattered radiation is measured at some angle (often 90 deg) with a suitable
spectrometer. At the very most, the intensities of Raman lines are 0.001 % of the
intensity of the source; as a consequence, their detection and measurement are
somewhat more difficult than are infrared spectra.
A Raman spectrum can be obtained by irradiating a sample of carbon tetrachloride (Fig
18-2) with an intense beam of an argon ion laser having a wavelength of 488.0 nm
(20492 cm-1). The emitted radiation is of three types:
1. Stokes scattering
2. Anti-stokes scattering
3. Rayleigh scattering

19. Contd…
 The abscissa of Raman spectrum is the
wavenumber shift , which is defined as the
difference in wavenumbers (cm-1) between the
observed radiation and that of the source.
 For CCl4 three peaks are found on both sides of
the Rayleigh peak and that the pattern of shifts
on each side is identical.
 Anti-Stokes lines are appreciably less intense
that the corresponding Stokes lines. For this
reason, only the Stokes part of a spectrum is
generally used. The magnitude of Raman shifts
are independent of the wavelength of
excitation.

20. Mechanism of Raman and Rayleigh Scattering
The heavy arrow on the far left depicts the energy change
in the molecule when it interacts with a photon. The
increase in energy is equal to the energy of the photon h.
The second and narrower arrow shows the type of change
that would occur if the molecule is in the first vibrational
level of the electronic ground state.

21. Mechanism of Raman and Rayleigh Scattering
The middle set of arrows depicts the changes that
produce Rayleigh scattering. The energy changes that
produce stokes and anti-Stokes emission are depicted on
the right. The two differ from the Rayleigh radiation by
frequencies corresponding to E, the energy of the first
vibrational level of the ground state. If the bond were
infrared active, the energy of its absorption would also be
E. Thus, the Raman frequency shift and the infrared
absorption peak frequency are identical.

22. Mechanism of Raman and Rayleigh Scattering
The relative populations of the two upper energy states are
such that Stokes emission is much favored over anti-Stokes.
Rayleigh scattering has a considerably higher probability of
occurring than Raman because the most probable event is
the energy transfer to molecules in the ground state and
reemission by the return of these molecules to the ground
state. The ratio of anti-Stokes to Stokes intensities will
increase with temperature because a larger fraction of the
molecules will be in the first vibrationally excited state
under these circumstances.

23. Raman vs. I.R
For a given bond, the energy shifts observed in a Raman
experiment should be identical to the energies of its
infrared absorption bands, provided that the vibrational
modes involved are active toward both infrared absorption
and Raman scattering. The differences between a Raman
spectrum and an infrared spectrum are not surprising.
Infrared absorption requires that a vibrational mode of the
molecule have a change in dipole moment or charge
distribution associated with it.

25. Raman vs. I.R
In contrast, scattering involves a momentary distortion of
the electrons distributed around a bond in a molecule,
followed by reemission of the radiation as the bond
returns to its normal state. In its distorted form, the
molecule is temporarily polarized; that is, it develops
momentarily an induced dipole that disappears upon
relaxation and reemission. The Raman activity of a given
vibrational mode may differ markedly from its infrared
activity.

26. Intensity of Normal Raman Peaks
The intensity or power of a normal Raman peak depends in
a complex way upon the polarizability of the molecule,
the intensity of the source, and the concentration of the
active group. The power of Raman emission increases with
the fourth power of the frequency of the source; however,
advantage can seldom be taken of this relationship
because of the likelihood that ultraviolet irradiation will
cause photodecomposition. Raman intensities are usually
directly proportional to the concentration of the active
species.

27. Raman Depolarization Ratios
Polarization is a property of a beam of radiation
and describes the plane in which the radiation
vibrates. Raman spectra are excited by plane-
polarized radiation. The scattered radiation is
found to be polarized to various degrees
depending upon the type of vibration responsible
for the scattering.

29. Raman Depolarization Ratios
The depolarization ratio p is defined as
Experimentally, the depolarization ratio may be obtained
by inserting a polarizer between the sample and the
monochromator. The depolarization ratio is dependent
upon the symmetry of the vibrations responsible for
scattering.
p
I
I




30. Raman Depolarization Ratios
Polarized band: p = < 0.76 for totally symmetric
modes (A1g)
Depolarized band: p = 0.76 for B1g and B2g
nonsymmetrical vibrational modes
Anomalously polarized band: p = > 0.76 for A2g
vibrational modes

34. INSTRUMENTATION
Instrumentation for modern Raman spectroscopy consists of three
components:
A laser source, a sample illumination system and a suitable
spectrometer.
Source
The sources used in modern Raman spectrometry are nearly always
lasers because their high intensity is necessary to produce Raman
scattering of sufficient intensity to be measured with a reasonable
signal-to-noise ratio. Because the intensity of Raman scattering
varies as the fourth power of the frequency, argon and krypton ion
sources that emit in the blue and green region of the spectrum have
and advantage over the other sources.

38. Sample Illumination System
Sample handling for Raman spectroscopic measurements is
simpler than for infrared spectroscopy because glass can be
used for windows, lenses, and other optical components
instead of the more fragile and atmospherically less stable
crystalline halides. In addition, the laser source is easily
focused on a small sample area and the emitted radiation
efficiently focused on a slit. Consequently, very small samples
can be investigated. A common sample holder for nonabsorbing
liquid samples is an ordinary glass melting-point capillary.

39. Sample Illumination System
 Liquid Samples: A major advantage of sample handling in Raman
spectroscopy compared with infrared arises because water is a
weak Raman scatterer but a strong absorber of infrared radiation.
Thus, aqueous solutions can be studied by Raman spectroscopy but
not by infrared. This advantage is particularly important for
biological and inorganic systems and in studies dealing with water
pollution problems.
 Solid Samples: Raman spectra of solid samples are often acquired
by filling a small cavity with the sample after it has been ground to
a fine powder. Polymers can usually be examined directly with no
sample pretreatment.

40. Raman Spectrometers
Raman spectrometers were similar in design and used the
same type of components as the classical ultraviolet/visible
dispersing instruments. Most employed double grating
systems to minimize the spurious radiation reaching the
transducer. Photomultipliers served as transducers. Now
Raman spectrometers being marketed are either Fourier
transform instruments equipped with cooled germanium
transducers or multichannel instruments based upon
charge-coupled devices.

43. APPLICATIONS OF RAMAN SPECTROSCOPY
Raman Spectra of Inorganic Species
The Raman technique is often superior to infrared for
spectroscopy investigating inorganic systems because aqueous
solutions can be employed. In addition, the vibrational energies
of metal-ligand bonds are generally in the range of 100 to 700
cm-1, a region of the infrared that is experimentally difficult to
study. These vibrations are frequently Raman active, however,
and peaks with  values in this range are readily observed.
Raman studies are potentially useful sources of information
concerning the composition, structure, and stability of
coordination compounds.

44. Raman Spectra of Organic Species
Raman spectra are similar to infrared spectra in that they have
regions that are useful for functional group detection and fingerprint
regions that permit the identification of specific compounds. Raman
spectra yield more information about certain types of organic
compounds than do their infrared counterparts.
Biological Applications of Raman Spectroscopy
Raman spectroscopy has been applied widely for the study of
biological systems. The advantages of his technique include the
small sample requirement, the minimal sensitivity toward
interference by water, the spectral detail, and the conformational
and environmental sensitivity.

45. Quantitative applications
Raman spectra tend to be less cluttered with peaks than
infrared spectra. As a consequence, peak overlap in
mixtures is less likely, and quantitative measurements are
simpler. In addition, Raman sampling devices are not
subject to attack by moisture, and small amounts of water
in a sample do not interfere. Despite these advantages,
Raman spectroscopy has not yet been exploited widely for
quantitative analysis. This lack of use has been due largely
to the rather high cost of Raman spectrometers relative to
that of absorption instrumentation.

46. Resonance Raman Spectroscopy
Resonance Raman scattering refers to a phenomenon in
which Raman line intensities are greatly enhanced by
excitation with wavelengths that closely approach that of
an electronic absorption peak of an analyte. Under this
circumstance, the magnitudes of Raman peaks associated
with the most symmetric vibrations are enhanced by a
factor of 102 to 106. As a consequence, resonance Raman
spectra have been obtained at analyte concentrations as
low as 10-8 M.

48. Resonance Raman Spectroscopy
The most important application of resonance Raman spectroscopy
has been to the study of biological molecules under physiologically
significant conditions; that is , in the presence of water and at low
to moderate concentration levels. As an example, the technique
has been used to determine the oxidation state and spin of iron
atoms in hemoglobin and cytochrome-c. In these molecules, the
resonance Raman bands are due solely to vibrational modes of the
tetrapyrrole chromophore. None of the other bands associated
with the protein is enhanced, and at the concentrations normally
used these bands do not interfere as a consequence.

49. Surface-Enhanced Raman Spectroscopy (SERS)
Surface enhanced Raman spectroscopy involves obtaining Raman
spectra in the usual way on samples that are adsorbed on the surface
of colloidal metal particles (usually silver, gold, or copper) or on
roughened surfaces of pieces of these metals. For reasons that are
not fully understood, the Raman lines of the adsorbed molecule are
often enhanced by a factor of 103 to 106. When surface enhancement
is combined with the resonance enhancement technique discussed in
the previous section, the net increase in signal intensity is roughly the
product of the intensity produced by each of the techniques.
Consequently, detection limits in the 10-9 to 10-12 M range have been
observed.